Study On Synthesis And Properties Of Functionalized Resorcinarenes

Calix[n]arenes are known as the third generation supramolecular hosters and the molecular design and chemical applications of them have become the most hot research field in supramolecular chemistry and others. Calix[4]resorcinarenes or resorcinarenes also represent an public platform of host-guest chemistry and have versatile applications in supramolecular chemistry such as coordination chemistry, molecular recognition, supramolecular self-assembly, molecular devices, chemical sensors, liquid crystal and nanomaterials. As the continuation of our research on calixarene with the aim of functional modification, supramolecular self-assembly and catalytic properties, in this text we initiated the studies on the synthesis, molecular structures and properties of some functionalized resorcinarene derivatives, and have achieved a series of significant and creative results. The main results are showed as follows:1. With methyl, 0-hydroxyphenyl, and 3-methox-4-hydroxyphenyl resorcinarenes as starting materials and through acylation and alkylation reactions of phenolic hydroxyl groups of resorcinarenes, a series of resorcinarenes with functionalized ester, etherester, tosylate, chloropropyl, cyanopropyl groups have been synthesized. Their structures are characterized by IR, ¹H NMR and ¹³C NMR and were further confirmed by determination of seven representative single crystals.2. A novel and efficient method of preparation of alkyl resorcinarylacetate was successfully developed, which are key intermediates in the chemical modification of resorcinarenes. Under the catalysis of boron trifluoride etherate aliphatic or aromatic aldehydes cyclocondensated with 1,3-(dialkoxy)benzenes in methylene dichloride directly produced alkyl resorcinarylacetates in high yields. Their structures are also characterized by IR, ¹H NMR, ¹³C NMR and confirmed by determination of three single crystals.3. The efficient introduction methods of functional pyridyl groups into resorcinarene were investigated. Through the ammonolysis of ethyl resorcinarylacetates with 2-, 4-aminomethylpyridine in high temperature, eight resorcinarenes with functional pyridyl amide groups were prepared in satisfied yields. By esterification of reorcinarenes with 2-, 3-, 4-pyridylformyl chloride, several resorcinarenes having eight or twelve pyridylformate groups were synthesized. Their structures are fully characterized by IR, ¹H NMR, ¹³C NMR and confirmed by determination of two single crystals.4. Through the ammonolysis of ethyl resorcinarylacetates with hydrated hydrazine, ethylenediamine and other diaminoalkanes, resorcinarene amides with terminal free amino groups are produced. Then by the condensation reaction of the latters with salicylaldhyde, pyridinecarboaldehyde, a series of resorcinarene Schiff base ligands with eight or twelve functional imino groups have prepared efficiently. The structures of these polydentated Schiff bases were preliminarily characterized by IR, ^<sup>1H NMR.